Solid formulations of agrochemicals

ABSTRACT

New solid formulations of A) at least one agrochemical active compound, B) at least one additive from the groups mentioned in the description, C) at least one dispersant, D) at least one carrier and E) if appropriate, further active compounds and/or additives, a process for preparing the solid formulations and their use for treating plants. A new device for preparing new granules.

This is a division of application Ser. No. 911,992, filed Jul. 10, 1992,now U.S. Pat. No. 5,230,892 which is a continuation of Ser. No. 746,393,now abandoned.

The present invention relates to new solid formulations based onagrochemical active compounds, to processes for the preparation of thesolid formulations and to their use as agents for treating plants.

It has already been disclosed that agrochemical active compounds can beused in the form of solid formulations, such as granules or powders.However, the activity of such preparations is not always entirelysatisfactory. For example, it is in some cases less powerful than thatof corresponding emulsifiable concentrates.

In particular, it has already been disclosed that1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-olhas fungicidal properties and can be converted into customaryformulations (cf. EP-OS (European Published Specification) 0,040,345).Thus, solid formulations, such as granules or powders, which contain theabove-mentioned active compound, can also be produced. The activity andthe compatibility of these conventional solid formulations, however, isnot always entirely satisfactory.

Furthermore, the production of granules containing agrochemical activecompounds by the fluidised-bed process has also been described (cf.EP-OS (European Published Specification) 0,163,836). Thus, it is alsopossible using this method, to obtain granules in which1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-olis present as the active component. However, the activity of theseformulations too, leaves something to be desired in some cases.

New solid formulations of

A) at least one agrochemical active compound,

B) at least one additive from the groups comprising

polyethoxy-isotridecylalcohol having an average of 6 ethylene oxideunits per molecule, or

alkylaryl-polyethoxyethanol phosphoric acid esters, or

the N-alkyl-lactams of the formula ##STR1## in which R represents alkylhaving 6 to 18 carbon atoms and

n represents the numbers 3, 4 or 5, or

the N,N-dimethyl-alkylcarboxamides of the formula ##STR2## in which R¹represents alkyl having 5 to 11 carbon atoms,

C) at least one dispersant,

D) at least one carrier and

E) if appropriate, further active compounds and/or additives, have nowbeen found.

Furthermore, it has been found that the new solid formulations can beprepared by either

a)--introducing a solution of at least one agrochemical active compoundand, if appropriate, additives in at least one additional compound fromamongst the groups mentioned under (B) and

a mixture of at least one dispersant and at least one carrier and, ifappropriate, further agrochemical active compounds and/or additives,separately into a fluidised-bed granulator, granulating the mixtureuntil a granular product has formed, and discharging the granules fromthe fluidised-bed granulator, if appropriate after spraying with waterfollowed by drying, or

b)--introducing a mixture of at least one dispersant and at least onecarrier and, if appropriate, agrochemical-active compounds and/oradditives into a mixer,

spraying into the mixer a solution of at least one agrochemical activecompound and, if appropriate, additives in at least one additionalcompound from amongst the groups mentioned under (B) until a producthaving the desired particle size is formed and

discharging the resulting solid formulation from the mixer, ifappropriate, after previously spraying with water followed by drying,and, if appropriate, subsequently grinding the resulting solidformulations.

Furthermore, it has been found that the solid formulations according tothe invention can be employed very successfully as agents for treatingplants and have excellent biological properties.

Finally, a new device for preparing the new granules has been found. Thedevice essentially consists of a fluidised-bed granulator whichcomprises

one or more feed pipes for feeding a solid phase to the fluidised bed,

one or more two-fluid nozzles for feeding and for atomising a liquidphase,

one or more feed pipes for feeding fluidising gas and

one or more counterflow gravity classifiers for discharging granules.

It must be considered extremely surprising that the solid formulationsaccording to the invention in all cases have superior biologicalproperties to the corresponding solid formulations hitherto known. Thus,for example, the solid formulations according to the invention, based on1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)pentan-3-ol can be used considerably more effectively for combatingphytopathogenic fungi than the solid formulations known from the priorart and which also contain the same active compound.

Agrochemical active compounds which can be contained in the solidformulations according to the invention are all those substances whichare conventionally suitable for treating plants. Suitable activecompounds are not only substances which are solid at room temperaturebut also those which are liquid at room temperature. The onlyprecondition for the use of liquid components is that they must becapable of being applied to solid carrier substances, if appropriate,with powdering. The active components can be soluble or insoluble inwater. They must have such stability that they do not undergo any majordecomposition while the process according to the invention is beingcarried out or during the use of the resulting solid formulations.

In the present case, agrochemical active compounds are to be understoodto be active compounds which are customarily usable in crop protection.They preferably include insecticides, acaricides, nematicides,fungicides, herbicides, growth regulators and fertilisers. The followingmay be mentioned as specific examples of such active compounds.

1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pental-3-ol(tubuconazole),1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol(triadimenol),1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one(triadimefon),1-(4-phenyl-phenoxy)-3,3-dimethyl-(1,2,4-triazol-1-yl)-butan-2-ol(bitertanol),N,N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)-sulphamide(dichlofluanid),N,N-dimethyl-(N'-fluorodichloromethylthio)-N'-(4-methylphenyl)-sulphamide(tolylfluanid),N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide (captan),N-(1,1,2,2-tetrachloroethyl-sulphenyl)-cis-4-cyclohexene-1,2-dicarboxamide(captafol), N-trichloromethylthio-phthalimide (folpet),N-dodecyl-guanidine acetate (dodine), tetrachloro-isophthalonitrile(chlorothalonil), 4,5,6,7-tetrachlorophthalide, zincethylene-bis-dithiocarbamate (zineb), manganeseethylene-bis-dithiocarbamate (maneb), zincethylene-bis-dithiocarbamate/manganese ethylene-bis-dithiocarbamate(mancozeb), zinc propylene-1,2-bis-dithiocarbamate (propineb),1-[3-(4-(1,1-dimethylethyl)-phenyl)-2-methylpropyl]-piperidine(fenpropidin), N-tridecyl-2,6-dimethyl-morpholine (tridemorph),N-dodecyl-2,6-dimethyl-morpholine (aldimorph),2-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-imidazole (imazalil),N-[2-(2,4,6-trichlorophenoxy)-ethyl]-N-propyl-1H-imidazole (prochloraz),N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide(procymidone), 2-methoxycarbamoyl-benzimidazole (carbendazim), methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl),2,4-dichloro-6-(2'-chlorophenyl-amino)-1,3,4-triazine (anilazine),bis-(8-guanidino-octyl)-amine triacetate (guazatine),1-(4-chlorobenzyl)-1-cyclopentyl-3-phenyl-urea (pencycuron),6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline (chinomethionat),trans-4-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-3-thiazolidin-carboxamide(hexythiazox),1-(4-fluorophenyl)-1-(1,2,4-triazol-1-yl-methyl)-2-(2-chlorophenyl)-oxirane,2-(2,4-dichlorphenyl)-1-(1,2,4-triazol-1-yl)-pentane (penconazole),1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-(1,2,4-triazole)(propiconazole),1-(2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4-methyl-(1,3-dioxolan-2-yl)-methyl]-1H(1,2,4-triazole),1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-ol(diclobutrazole),1-(2-chlorophenyl)-2-(1-chloro-cycloprop-1-yl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,1-cyclohexyl-4,4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-yl)-pent-1-ene(triapenthenol), 2-iospropoxy-phenyl-N-methyl-carbamate,4-amino-6-(1,1-dimethyl-ethyl)-3-methylthio-1,2,4-triazin-5(4H)-on(metribuzin), 3-methyl-4-amino-6-phenyl-1,2,4-triazin-5(4H)-on(metamitron), N-benzthiazolyl-N-methyl-N'-methyl-urea,3-methoxycarbonyl-aminophenyl-N-(3'-methyl-phenyl)-carbamate,N-(4-trifluoromethoxy-phenyl)-N'-(2-chloro-benzoyl)-urea,1-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-3-(4-phenyl-1,2,5-oxadiazol-3-yl)-urea,2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-methansulfonate,1-(4-Chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-olof the formula ##STR3## is particularly preferred.

This active compound and its use as a fungicide are known (cf.; EP-OS(European Published Specification) 0,040,345).

The active compound of the formula (I) can be contained in the solidformulations according to the invention either as the sole activecomponent or in admixture with other agrochemical active compounds.

In the solid formulations according to the invention, at least one ofthe substances mentioned under (B) is contained as an additionalsubstance. The following are preferably suitable:

polyethoxy-iso-tridecyl alcohol having an average of 6 ethylene oxideunits per molecule,

alkylaryl-polyethoxethanol phosphoric acid ester, commercially availableunder the name "Blendex®",

N-alkyl-lactams of the formula (II) in which

R represents alkyl having 8 to 14 carbon atoms and

n represents the numbers 3, 4 or 5, and

moreover, individual N,N-dimethyl-alkylcarboxamides of the formula(III), or mixtures thereof.

Particularly preferred N-alkyl-lactams are those substances of theformula (II) in which

R represents alkyl having 8, 10 or 12 carbon atoms and

n represents the numbers 3, 4 or 5.

The following may be mentioned as examples of N-alkyl-lactams of theformula (II):

N-dodecyl-caprolactam

N-decyl-caprolactam

N-octyl-caprolactam

N-dodecyl-pyrrolidone

N-decyl-pyrrolidone

N-octyl-pyrrolidone

N-dodecyl-valerolactam

N-decyl-valerolactam

N-octyl-valerolactam.

Also particularly preferred is the mixture ofN,N-di-methyl-alkylcarboxamides of the formula (III) which is knownunder the tradename Hallcomid and which comprises, on average, 5%N,N-dimethyl-hexanecarboxamide, 50% N,N-dimethyl-octanecarboxamide, 40%N,N-dimethyl-decanecarboxamide and 5% N,N-dimethyl-dodecanecarboxamide.

The additional substances present in the solid formulations according tothe invention are known (cf. J. Org. Chem. 18, 1087 (1953); Ann. Chem.596, 203 (1955); J. Amer. Chem. Soc. 69, 715 (1947); DE-AS (GermanPublished Specification) 1,160,268; EP-OS (European PublishedSpecification) 0,077,078, WO 88/00 184 and Farm Chemicals Handbook 1990,C 44).

Suitable dispersants in the case of solid formulations according to theinvention are all substances which have appropriate surface-activeproperties and which can customarily be employed for such purposes. Thefollowing are preferred; ligninsulphonates such as lithium salts, sodiumsalts, potassium salts, magnesium salts, calcium salts and ammoniumsalts of ligninsulphonic acid, furthermore condensation products ofaryl- or alkylaryl-sulphonic acids and formaldehyde, such ascondensation products of sulphonated ditolyl ether and formaldehyde, andsalts thereof, as well as addition products of ethyleneoxide and fattyacid esters and salts thereof.

Suitable carriers in the case of the solid formulations according to theinvention are all solid substances which have a large surface areaand/or high absorbency and which can customarily be used in granules andpowders. The following are preferred; ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomacious earth, and ground synthetic minerals such ashighly-disperse silica, alumina and silicates, and furthermore saltssuch as potassium sulphate, potassium carbonate and sodium hydrogencarbonate.

Suitable additive which can be contained in the solid formulationsaccording to the invention are binders, preservatives, colorants, acidsand granulation liquids.

Binders which can be contained are all binders (tackifiers) which arecustomarily present in water-dispersible solid formulations. Thefollowing are preferably suitable in this context: methylcellulose,sugars, dextrin, starch, alginates, glycols, polyvinyl pyrrolidone,ligninsulphonate, gum arabic, polyvinyl alcohol and polyvinyl acetate.

Examples of preservatives which can be contained in the solidformulations according to the invention are 2-hydroxybiphenyl, sorbicacid, p-hydroxybenzaldehyde, methyl p-hydroxybenzoate, benzaldehyde,benzoic acid and propyl p-hydroxybenzoate.

Colorants which may be mentioned as suitable additives are inorganicpigments such as iron oxide, titanium dioxide and Prussian blue, andorganic dyestuffs such as alizarin, azo and metal phthalocyaninedyestuffs.

An example of an acid which may be mentioned as a suitable additive isp-tolyl-sulphonic acid.

Examples of granulation liquids which can be contained in the solidformulations according to the invention are water, organic solvents ormixtures of water and organic solvents. Preferred organic solvents whichare suitable in this context are alcohols such as ethanol and glycol,halogenohydrocarbons such as methylene chloride, and ethers such asdioxane and tetrahydrofuran. Water is particularly preferred asgranulation liquid.

In the solid formulations according to the invention, the percentagecontents of the components can be varied within substantial range. Ingeneral, the content of agrochemical active compounds is between 5 and90% by weight, preferably between 10 and 50%by weight. The amount ofadditive is generally 5 to 75% by weight, preferably 10 to 70% byweight. The amount of dispersant is generally between 1 and 30% byweight, preferably between 5 and 25% by weight; and the amount ofcarrier is generally between 10 and 50% by weight, preferably between 15and 45% by weight. The additional compounds are generally contained inamounts of between 10 and 70% by weight, preferably between 20 and 50%by weight, and the amount of granulation liquid is generally between 0and 3.5% by weight.

When carrying out the process according to the invention by means ofvariants (a) or (b), all those components can preferably be used asbeing preferred which have already been mentioned in connection with thedescription of the solid formulations according to the invention.

For carrying out the process according to the invention by means ofvariant (a), a solution of at least one agrochemical active compoundand, if appropriate, additional substances in at least one additive isfirst prepared. For this purpose,the components are stirred with eachother at temperatures between 10° C. and 100° C., preferably between 20°C. and 90° C., so that a liquid phase results. Accordingly, the liquidphase is a melt or a true solution.

Furthermore, a solid mixture is prepared by mixing at least onedispersant and, if appropriate, one or more agrochemical activecompounds and/or additives with at least one solid carrier in such aratio that the resulting mixture is in the solid phase. This mixture ofsolid substances is homogenised using customary processes.

For carrying out the process according to the invention by means ofvariant (a), the liquid and the solid phase are introduced separatelyinto a fluidised-bed granulator. In general, a procedure is followed inwhich the solid, finely pulverulent phase is passed into the granulatorthrough one or more inlets and fluidised with the aid of a stream ofgas. The liquid phase is also sprayed into the granulator through one ormore separate nozzles. The liquid phase is preferably added via one ormore two-fluid nozzles which are constructed in such a way that theliquid phase is transported through a first line and a stream of gas(atomising gas) is fed in through a second line. Both streams meet eachother at the end of the nozzle in such a way that, with the aid of theatomising gas, the liquid phase is sprayed into the fluidised bed in theform of small droplets, and there meets the particles of the solidphase.

If appropriate, post-granulation can be carried out by spraying onwater. To remove water and/or other solvents, the granules can be driedwith the aid of the stream of gas for fluidisation.

When carrying out the process according to the invention by means ofvariant (a), the temperatures can be varied within a substantial range.For example, the process is carried out using a liquid phase whosetemperature is between 10° C. and 100° C., preferably between 20° C. and90° C. The solid phase is fed in at temperatures between 10° C. and 50°C., preferably between 20° C. and 40° C. The temperature of the streamof gas for fluidisation is between 20° C. and 250° C., preferablybetween 40° C. and 200° C. The temperature of the stream of gas foratomisation, which enters through the two-fluid nozzle, is between 0° C.and 100° C., preferably between 10° C. and 90° C.

To produce the fluidised bed, all gases which are customarily employedfor such purposes can be used. Air or nitrogen are preferably suitable.

For spraying in the liquid phase via one or more two-fluid nozzles, itis also possible to use all gases which are customary for such purposes.Air or nitrogen are preferably suitable.

The finished granules can be discharged from the granulator viacustomary withdrawal devices. Counter-current gravity classifiers arepreferably used.

The product obtained can subsequently be postgranulated and/or driedand/or ground.

When variant (a) is used, the process according to the invention can becarried out continuously or batchwise.

The device for preparing the granules according to variant (a) of theinvention is a fluidised-bed granulator which differs from thepreviously known apparatuses of this essentially by the fact that theliquid phase and the finely pulverulent solid phase are fed separatelyinto the fluidised bed.

One or more feedpipes for the solid phase are located in the lower areaof the fluidised bed, preferably in the side wall of the apparatus,slightly above the inlet-flow bottom. To feed the liquid phase, thereexist one or more two-fluid nozzles which are preferably arranged at theinlet-flow bottom. The two-fluid nozzles are constructed in such a waythat the liquid phase is transported through the first feedpipe and astream of gas (atomising gas) is fed through a second feedpipe. One ormore feedpipes for introducing fluidised gas are arranged below theinlet-flow bottom. Finally, the device contains one or more counterflowgravity classifiers for discharging granules. The counterflow gravityclassifiers are preferably built into the inlet-flow bottom. Preferredcounterflow gravity classifiers which are suitable are so-called zig-zagclassifiers.

Variant (a) of the process according to the invention is preferablycarried out in a fluidised-bed granulator as shown in FIG. 1 in the formof a diagram. In this figure,

1 denotes the wall of the granulator vessel,

2 denotes the feed for the solid phase,

3 denotes the feed for the liquid phase,

4 denotes the feed for the atomising gas,

5 denotes the two-fluid nozzle,

6 denotes the feed for the fluidised gas,

7 denotes the fluidised bed,

8 denotes the settle zone in the fluidised bed,

9 denotes the counterflow gravity classifier, and

10 denotes the withdrawal device for the granules.

For carrying out the process according to the invention by means ofvariant (b), a solid mixture is first prepared by mixing at least onedispersant and, if appropriate, one or more agrochemical activecompounds and/or additional compounds with at least one solid carrier insuch a ratio that the resulting mixture is in the solid phase. Thismixture of solid substances is homogenised and ground using customaryprocesses.

Furthermore, a solution of at least one agrochemical active compoundand, if appropriate, additional substances in at least one additive isprepared. For this purpose, the components are stirred with each otherat temperatures between 10° C. and 100° C., preferably between 20° C and90° C., so that a liquid phase results. Accordingly, the liquid phase isa melt or a true solution.

For carrying out the process according to the invention by means ofvariant (b), the solid, finely pulverulent phase is passed into a mixerand sprayed with the liquid phase. In general, a procedure is followed,in which the liquid phase is sprayed into the mixer through one or moreseparate nozzles.

The liquid phase is preferably added via one or more two-fluid nozzleswhich are constructed in such a way that the liquid phase is transportedthrough a first line and a stream of gas (atomising gas) is fed inthrough a second line. Both streams meet each other at the end of thenozzle in such a way that, with the aid of the atomising gas, the liquidphase is sprayed into the mixer in the form of small droplets, and theremeets the particles of the solid phase.

If appropriate, a post-treatment can be carried out by spraying onwater. To remove water and/or other solvents, the resulting solidformulation can be dried by customary methods.

When carrying out the process according to the invention by means ofvariant (b), the temperatures can also be varied within a substantialrange. For example, the process is carried out using a liquid phasewhose temperature is between 10° C. and 100° C., preferably between 20°C. and 90° C. The solid phase is kept at temperatures between 10° C. and50° C., preferably between 20° C. and 40° C. The temperature of thestream of gas for atomisation, which enters through the two-fluidnozzle, is between 0° C. and 100° C., preferably between 10° C. and 90°C.

For spraying the liquid phase into the mixer via one or more nozzles, itis again possible to use all gases which are customary for suchpurposes. Air or nitrogen are preferably suitable.

For carrying out the process according to the invention by means ofvariant (b), all mixers are suitable which are customary for suchpurposes. The resulting solid formulation can be discharged from themixer via customary withdrawal devices. The pulverulent or granularproduct obtained can subsequently be subjected to customary grinding orgranulation.

When using variant (b), the process according to the invention can alsobe carried out continuously or discontinuously. In general, the processis carried out discontinuously by introducing the required componentsinto the mixer in batches.

When carrying out the process according to the invention by means ofvariant (a), uniformly shaped granules are obtained, whereas pulverulentor granular products are obtained when using variant (b). These productscan be comminuted by grinding by using devices which are customary forthis purpose.

The solid formulations according to the invention have a high stability.They have a compact, microporous structure and are neverthelessspontaneously dispersible or soluble in water or other solvents. Byspontaneous dispersibility, or solubility, is to be understood in thepresent case that the particles disperse, or dissolve, completely ingenerally 0.1 to 5 minutes, preferably in 0.2 to 3 minutes.

The solid formulations according to the invention contain one or moreagrochemical active compounds and can therefore be employed usingcustomary methods for the treatment of plants in agriculture andhorticulture. The solid formulations according to the invention are, forexample, dispersed in water. The dispersions formed in this process canbe applied by customary methods to the plants and/or their environment,that is to say, for example, by spraying, atomising or pouring, ifappropriate after previous dilution. The application rates in thiscontext depend on the concentration of the dispersion, on the particularindication and on the active components employed.

The preparation and use of the solid formulations according to theinvention are illustrated by the examples which follow.

PREPARATION EXAMPLES EXAMPLE 1

To prepare a liquid phase, 930 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3ol(97%) are dissolved completely at 60° C. in 2700 g ofpolyethoxyisotridecyl alcohol having an average of 6 ethylene oxideunits per molecule, with stirring.

Moreover, a finely pulverulent, solid phase is prepared by mixing 1200 gof a formaldehyde-crosslinked alkylaryl-sulphonate with 1170 g of highlydisperse silica in a small plough-bar mixer at room temperature, and themixture is homogenised.

The preparation of granules which follows is carried out in afluidised-bed granulator. For this purpose, the solid phase isintroduced into the granulator and fluidised by blowing in air at atemperature of 25° C. in an amount of 300 to 500 m³ /h. At the sametime, spraying of the liquid phase at 60° C. into the fluidised bed viaa two-fluid nozzle with the aid of air commences. After 60 minutes,spraying-in of the liquid phase is complete. After this, apost-granulation is carried out by spraying on 1600 g of water at 50°C., followed by drying to a residual moisture of 1% by weight of waterby heating the air which is passed in at 70° C. The granules formed areclassified. In this way, 5 kg of granules of particle sizes in the rangebetween 200 and 1500 μm are obtained. When 1 kg of these granules, whichcontain 1.5% by weight of active compound, are added to 200 l of water,spontaneous wetting takes place, and the granules are dissolvedcompletely within 10 seconds.

EXAMPLE 2

To prepare a liquid phase, 1550 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol(97%) are dissolved completely in a mixture of 900 g ofpolyethoxy-iso-tridecyl alcohol having an average of6 ethylene oxideunits per molecule and 1200 g of alkylaryl-polyethoxy-ethanol phosphoricacid ester, which is commercially available under the name "Blendex®",at 60° C. with stirring.

Moreover, a finely pulverulent solid phase is prepared by mixing 1200 gof a formaldehyde-crosslinked alkylarylsulfonate with 1150 g of highlydisperse silica in a small plough-bar mixer at room temperature andhomogenising the mixture.

The preparation of granules which follows is carried out in afluidised-bed granulator. For this purpose, the solid phase isintroduced into the granulator and fluidised by blowing in air at atemperature of 25° C. in an amount of 300 to 500 m³ /h. At the sametime, spraying of the liquid phase at 60° C. into the fluidised bed viaa two-fluid nozzle with the aid of air commences. After 60 minutes,spraying-in of the liquid phase is complete. After this,post-granulation is carried out by spraying on 1600 g of water at 50°C., followed by drying to a residual moisture of 1% by weight of waterby heating the air which is passed in at 70° C. The granules formed areclassified. In this way, 5 kg of granules of particle sizes in the rangebetween 200 and 1500 μm are obtained.

When 1 kg of these granules, which contain 2.5% by weight of activecompound, are added to 200 l of water, spontaneous wetting takes place,and the granules are dissolved completely within 10 seconds.

EXAMPLE 3

To prepare a liquid phase, 4640 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol(97%) are dissolved completely in 13,360 g of polyethoxyisotridecylalcohol with an average of 6 ethylene oxide units per molecule, at 60°C. with stirring.

Moreover, a finely pulverulent solid phase is prepared by mixing 6000 gof a formaldehyde-crosslinked alkylarylsulphonate with 6000 g of highlydisperse silica in a small plough-bar mixer at room temperature andhomogenising the mixture.

Granulation which then follows is carried out in a granulation apparatusof the type represented in FIG. 1. For this purpose, the solid phase isfed pneumatically to the fluidised-bed reactor via feedpipes 2 andfluidised by blowing in nitrogen at a temperature of 80° C., in anamount of 50 kg/h, via line 6. At the same time, the liquid phase at atemperature of 60° C., is sprayed in via the two-fluid nozzle 5 with theaid of nitrogen as the atomising gas. The streams of product arecontrolled in such a way that the solid phase is fed to the reactor inan amount of 1.2 kg/h and the liquid phase in an amount of 1.8 kg/h.From the fluidised bed 7 which forms, 3 kg/h of granules of an averageparticle size of 0.4 mm are continuously discharged via the counterflowgravity classifier 9 and the withdrawal device 10. In this manner, 28 kgof granules of a content of 15.0% by weight of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3olare obtained.

EXAMPLE 4

To prepare a liquid phase 130 g of6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline are dissolved completelyin 2500 g of polyethoxy-isotridecyl alcohol with an average of 6ethylene oxide units per molecule and 2500 g of N-octyl-pyrrolidone, at60° C. with stirring.

Moreover, a finely pulverulent solid phase is prepared by mixing 1000 gof rice starch and 1900 g of a formaldehyde-crosslinkedalkylarylsulphonate with 1900 g of highly disperse silica in a smallplough-bar mixer at room temperature and homogenising the mixture.

Granulation which then follows is carried out in a granulation apparatusof the type represented in FIG. 1. For this purpose, the solid phase isfed pneumatically to the fluidised-bed reactor via feedpipes 2 andfluidised by blowing in nitrogen at a temperature of 80° C., in anamount of 50 kg/h, via line 6. At the same time, the liquid phase at atemperature of 60° C., is sprayed in via the two-fluid nozzle 5 with theaid of nitrogen as the atomising gas. The streams of product arecontrolled in such a way that the solid phase is fed to the reactor inan amount of 1.2 kg/h and the liquid phase in an amount of 1.8 kg/h.From the fluidised bed 7 which forms, 3 kg/h of granules of an averageparticle size of 0.4 mm are continuously discharged via the counterflowgravity classifier 9 and the withdrawal device 10. In this manner, 9 kgof granules having a content of 1.3% by eight of6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline are obtained.

EXAMPLE 5

To prepare a liquid phase, 101.56 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-oland 7.54 g of 6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline, 104.5 gof a mixture of N,N-dimethyl-alkylcarboxamides which consists, onaverage, of 5% of N,N-dimethyl-hexanecarboxamide, 50% ofN,N-dimethyl-octanecarboxamide, 40%of N,N-dimethyl-decanecarboxamide and5% of N,N-dimethyl-dodecanecarboxamide, 52.5 g of polyethoxy-isotridecylalcohol with an average of 6 ethylene oxide units per molecule and 5 gof p-tolyl-sulphonic acid are completely dissolved with stirring at80°C.

In addition, a finely pulverulent solid phase is prepared by mixing156.5 g of highly disperse silica, 52.5 g of diphenylsulphonic acidformaldehyde condensate and 19.9 g of sodium dialkylnaphthyl-sulphonatein a plough-bar mixer at room temperature and homogenising the mixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed apt 80° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 500 g of agranular solid formulation is obtained, which is ground to a powder.

EXAMPLE 6

To prepare a liquid phase, 136.64 g of3-methyl-4-amino-6-phenyl-1,2,4-triazin-5(4H)-one and 30.0 g ofpolyethoxy-isotridecyl alcohol with an average of 6 ethylene oxide unitsper molecule are dissolved completely at 80° C. with stirring.

In addition, a finely pulverulent solid phase is prepared by mixing18.32 g of 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl sulphonate,18.60 g of 3-methoxycarbonyl-aminophenyl-N-(3'-methylphenyl)-carbamate,60.0 g of a diphenylsulphonic acid formaldehyde condensate, 30.0 g ofhighly disperse silica and 6.;44 g of kaolin in a plough-bar mixer atroom temperature and homogenising the mixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed at 80° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 300 g of agranular solid formulation is obtained, which is ground to a powder.

EXAMPLE 7

To prepare a liquid phase, 53.2g kg of1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,1,4-triazol-1-yl)-butan-2-one, 20kg of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxideunits per molecule, 20 kg of N-octyl-pyrrolidone and 20 kg of a mixtureof N,N-dimethyl-alkylcarboxamides which consists, on average, of 5% ofN,N-dimethyl-hexanecarboxamide, 50% of N,N-dimethyl-octanecarboxamide,40% of N,N-dimethyl-decanecarboxamide and 5% ofN,N-dimethyl-dodecanecarboxamide, are dissolved completely at 90° C.with stirring.

In addition, a finely pulverulent solid phase is prepared by mixing 4 kgof a wetting agent based on alkylaryl-sulphonate, 20 kg of adiphenyl-sulphonic acid formaldehyde condensate and 62.8 kg of highlydisperse silica in a plough-bar mixer at room temperature andhomogenising the mixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed at 90° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 200 kg of agranular solid formulation is obtained, which is ground to a powder.

EXAMPLE 8

To prepare a liquid phase, 26.3 kg of1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,1,4-triazol-1-yl)-butan-2-ol, 10kg of polyethoxy-isotridecyl alcohol with an average of 6 ethylene oxideunits per molecule, 10 kg of N-octyl-pyrrolidone and 10 kg of a mixtureof N,N-dimethyl-alkylcarboxamides which consists, on average, of 5% ofN,N-dimethyl-hexanecarboxamide, 50% of N,N-dimethyl-octanecarboxamide,40% of N,N-dimethyl-decanecarboxamide and 5% ofN,N-dimethyl-dodecanecarboxamide, are dissolved completely at 90° C.with stirring.

In addition, a finely pulverulent solid phase is prepared by mixing 2 kgof a wetting agent based on alkylaryl-sulphonate, 10 kg of adiphenyl-sulphonic acid formaldehyde condensate and 31.7 kg of highlydisperse silica in a plough-bar mixer at room temperature andhomogenising the mixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed at 90° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 100 kg of agranular solid formulation is obtained, which is ground to a powder.

EXAMPLE 9

To prepare a liquid phase, 25.5 kg of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3ol,10 kg of polyethoxy-isotridecyl alcohol with an average of 6 ethyleneoxide units per molecule, 10 kg of N-octyl-pyrrolidone and 10 kg of amixture of N,N-dimethyl-alkylcarboxamides which consists, on average, of5% of N,N-dimethyl-hexanecarboxamide, 50% ofN,N-dimethyl-octanecarboxamide, 40% of N,N-dimethyl-decancecarboxamideand 5% of N,N-dimethyl-dodecanecarboxamide, are dissolved completely at90° C. with stirring.

In addition, a finely pulverulent solid phase is prepared by mixing 2 kgof a wetting agent based on alkylaryl-sulphonate, 10 kg of adiphenyl-sulphonic acid formaldehyde condensate and 32.5 kg of highlydisperse silica in a plough-bar mixer at room temperature andhomogenising the mixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed at 90° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 100 kg of agranular solid formulation is obtained, which is ground to a powder.

EXAMPLE 10

To prepare a liquid phase, 10 g of1-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-3-(4-phenyl-1,2,5-oxadiazol-3-yl)-urea,30 g of an emulsifier based on alkylarylpolyglycol ether, 6 g of anethyleneoxide-dimethyl-siloxane block copolymer with Si-C bonds, 6 g ofthe sodium salt of coconut fatty acid 2-sulfethylester containing 10% offree coconut fatty acid are dissolved completely at 90° C. withstirring.

In addition, a finely pulverulent solid phase is prepared by mixing 12 gof adiphenyl-sulphonic acid formaldehyde condensate and 36 g of highlydisperse silica in a mixer at room temperature and homogenising themixture.

The preparation of the solid formulation which then follows is carriedout in such a manner that the liquid phase is sprayed at 90° C. via anozzle into the mixer onto the solid phase, which has a temperatureequal to room temperature, while stirring. In this manner, 100 g of agranular solid formulation is obtained, which is ground to a powder.

COMPARISON EXAMPLE A

A mixture of 2630 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol,2000 g of a formaldehyde-crosslinked alkylarylsulphonate, 300 g ofphospholipid and 5070 g of sodium hydrogen carbonate is comminuted in aplough-bar mixer to a particle size of about 1 mm, and the mixture ishomogenised. The mixture is then ground with the aid of an air-jet millto an average particle size of about 7 μm and remixed.

The resulting premix is processed in a commercially availablefluidised-bed granulator to give granules by moistening batches of 4.8kg of powder in the fluidised bed with 1.5 liters of water in the courseof 21 minutes at room temperature and subsequently drying the granulesby warming the inlet air to 70° C. in the course of 11 minutes, so thatthe residual water content in the granules is about 1% by weight. Thetemperature of the granules in this procedure remains below 40° C. Theresulting granules are classified using a cascade of vibrating screens.In this manner, 4.5 kg of granules having particle sizes in the rangebetween 200 and 1500 μm are obtained per batch.

The suspension stability of the granules, measured by CIPAC method MT168, is 84%. The wet-screen test on screens with mesh size 315, 250 and160 μm, respectively, carried out by CIPAC method MT 167 gives screeningresidues of less than 0.005%.

COMPARISON EXAMPLE B

A mixture of 2630 g of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol,2000 g of a formaldehyde-crosslinked alkylarylsulphonate, 300 g ofphospholipid and 5070 g of sodium hydrogen carbonate is stirred into10kg of water with the aid of a toothed-disk stirrer and the mixture isprecomminuted with a toothed colloid mill. It is then ground finely on abead mill whose throughput is 25 kg/h. An aqueous suspension of a solidscontent of 50% by weight is obtained. At a shear gradient of 1000/sec,the viscosity of the suspension is approx. 65 mPas; the average particlediameter is approx. 4 μm.

In an amount of 7 kg/h, the resulting suspension is sprayed throughnozzles into a fluidised-bed reactor with continuously classifyingproduct discharge. A stream of nitrogen in an amount of 92 kg/h is usedfor fluidising. The temperature of the stream of nitrogen is 90° C. Inthe fluidised bed which forms, a product temperature of below 40° C. isestablished. The granules discharged have a particle size of approx. 0.4mm. The residual moisture of the granules is 2.1% by weight of water.

The suspension stability of the granules, measured by CIPAC method MT168, is 98%. The wet-screen test on screens with mesh size 315, 250 and160 μm, respectively, carried out by CIPAC method MT 167, gives noscreening residues.

In the use examples which follow, the granules prepared were tested fortheir biological effectiveness.

USE EXAMPLE A Erysiphe Test (barley)/curative

To prepare a suitable preparation of active compound, 1 part by weightof the particular granules is mixed with water, and the resultingconcentrate is diluted with water to the desired concentration.

To test for curative effectiveness, young plants are dusted with sporesof Erysiphe graminis f.sp. hordei.48 hours after the inoculation, theplants are sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of approx. 20° C.and a relative atmospheric humidity of approx. 80% to allow thedevelopment of mildew pustules.

The evaluation is carried out 7 and 14 days after the inoculation.

The formulations and concentrations of active compound, and the testresults, can been seen from the table below.

                  TABLE A                                                         ______________________________________                                        Erysiphe Test (barley)/curative                                                                           Degree of                                                                     effective-                                                                    ness in %                                                      Active compound                                                                              of the un-                                        Granules     concentration in                                                                             treated                                           of           the spray mixture                                                                            control                                           Example      in mg/l        7 d      14 d                                     ______________________________________                                        Known:                                                                        (A)          150            0        0                                        (B)          150            0        0                                        According to the                                                              invention                                                                     (1)          150            80       75                                       (2)          150            49       15                                       (3)          150            88       60                                       ______________________________________                                    

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

What is claimed is:
 1. A process for the preparation of a solidformulation consisting ofA) at least one agrochemically active compoundselected from the group consisting ofi) a fungicide selected from thegroup consisting of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol(tebuconazole),1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol(triadimenol), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one (triadimefon),1-(4-phenyl-phenoxy)-3,3-dimethyl-(1,2,4-triazol-1-yl)-butane-2-ol(bitertanol),N,N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)-sulphamide(dichlofluanid),N,N-dimethyl-(N'-fluorodichloromethylthio)-N'-(4-methylphenyl)-sulphamide(tolylfluanid),N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide (captan),N-(1,1,2,2-tetrachloroethyl-sulphenyl)-cis-4-cyclohexene-1,2-dicarboxamide(captafol), N-trichloromethylthio-phthalimide (folpet),N-dodecyl-guanidine acetate (dodine), tetrachloro-isophthalonitrile(chlorothalonil), 4,5,6,7-tetrachlorophthalide, zincethylene-bis-dithiocarbamate (zineb), manganeseethylene-bis-dithiocarbamate (maneb), zincethylene-bis-dithiocarbamate/manganese ethylene-bis-dithiocarbamate(mancozeb), zinc propylene-1,2-bis-dithiocarbamate (propineb),1-[3-(4-(1,1-dimethylethyl)-phenyl)-2-methylpropyl]-piperidine(fenpropidin), N-tidecyl-2,6-dimethyl-morpholine (tridemorph),N-dodecyl-2,6-dimethyl-morpholine (aldimorph),2-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-imidazole (imazalil),N-[2-(2,4,6-trichlorophenoxy)-ethyl]-N-propyl-1H-imidazole (prochloraz),N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide(procymidone), 2-methoxycarbamoyl-benzimidazole (carbendazim), methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl),2,4-dichloro-6-(2'-chlorophenyl-amino)-1,3,4-triazine (anilazine),bis-(8-guanidino-octyl)-amine triacetate (guazatine),1-(4-chlorobenzyl)-1-cyclopentyl-3-phenyl-urea (pencycuron),6-methyl-2-oxo-1,3-dithiolo-[4,5-b]-quinoxaline (chinomethionat),1-(4-fluorophenyl)-1-(1,2,4-triazol-1-yl-methyl)-2-(2-chlorophenyl)-oxirane,2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-pentane (pencoazole),1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-(1,2,4-triazole)(propiconazole),1-(2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4-methyl-(1,3-dioxolan-2-yl)-methyl]-1H-(1,2,4-triazole),1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-ol(diclobutrazole) and1-(2-chlorophenyl)-2-(1-chloro-cycloprop-1-yl)-3-(1,2,4-triazol-1-yl)-propan-2-ol;ii) a herbicide selected from the group consisting of4-amino-6-(1,1-dimethyl-ethyl)-3-methylthio-1,2,4-triazin-5(4H)-on(metribuzin), 3-methyl-4-amino-6-phenyl-1,2,4-triazin-5(4H)-onmetamitron), and N-benzthiazolyl-N-methyl-N'-methyl-urea and3-methoxycarbonyl-aminophenyl-N-(3'-methyl-phenyl)-carbamate, iii) aninsecticide selected from the group consisting of2-iospropoxy-phenyl-N-methyl-carbamate,N-(4-trifluoromethoxy-phenyl)-N'-(2-chloro-benzoyl)-urea,1-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-3-(4-phenyl-1,2,5-oxadiazol-3yl)-ureaand 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-methansulfonate,iv)trans-4-(4-chlorophenyl-N-cyclohexyl-4-methyl-2-oxo-3-thiazolidin-carboxamide(hexythiazox) and v)1-cyclohexyl-4,4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-yl)-pent-1-ene(triapenthenol), B) at least one additive selected from the groupconsisting ofi) polyethoxy-isotridecylalcohol having an average of 6ethylene oxide units per molecule, ii) an alkylaryl-polyethoxyethanolphosphoric acid ester, iii) an N-alkyl-lactam of the formula ##STR4## inwhich R represents alkyl having 6 to 18 carbon atoms and n representsthe numbers 3, 4 or 5, andiv) an N,N-dimethyl-alkylcarboxamide of theformula ##STR5## in which R¹ represents alkyl having 5 to 11 carbonatoms, C) at least one dispersant selected from the group consisting ofligninsulphonates, condensation products or aryl- or alkylaryl-sulphonicacids and formaldehyde, and addition products of ethyleneoxide and fattyacid esters and salts thereof, and D) at least one carrier selected fromthe group consisting of ground natural minerals and ground syntheticminerals, which process comprisesa) introducing a solution of at leastone agrochemical active compound (A) and optionally (E) in at least oneadditive (B) and a mixture of at least one dispersant (C) and at leastone carrier (D) and optionally (E), separately into a fluidized-bedgranulator, granulating the mixture until a granular product has formed,and discharging the granules from the fluidized-bed granulator,optionally after spraying with water followed by drying, and optionallysubsequently grinding the resulting solid formulation.
 2. A processaccording to claim 1, wherein the agrochemically active compound (A) isa fungicide selected from the group consisting of1-(4-chlorophenyl)-4,4-dimethyl-3-(1,2,4-triazol-1-yl-methyl)-pentan-3-ol(tebuconazole),1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl-butan-2-ol(triadimenol),1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one(triadimefon),1-(4-phenyl-phenoxy)-3,3-dimethyl-(1,2,4-triazol-1-yl)-butane-2-ol(bitertanol),N,N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)-sulphamide(dichlofluanid),N,N-dimethyl-(N'-fluorodichloromethylthio)-N'-(4-methylphenyl)-sulphamide(tolylfluanid),N-trichloromethylmercapto-4-cyclohexene-1,2-dicarboxamide (captan),N-(1,1,2,2-tetrachloroethyl-sulphenyl)-cis-4-cyclohexene-1,2-dicarboxamide(captafol), N-trichloromethylthio-phthalimide (folpet),N-dodecyl-guanidine acetate (dodine), tetrachloro-isophthalonitrile(chlorothalonil), 4,5,6,7-tetrachlorophthalide, zincethylene-bis-dithiocarbamate (zineb), manganeseethylene-bis-dithiocarbamate (maneb), zincethylene-bis-dithiocarbamate/manganese ethylene-bis-dithiocarbamate(mancozeb), zinc propylene-1,2-bis-dithiocarbamate (propineb),1-[3-(4-(1,1-dimethylethyl)-phenyl)-2-methylpropyl]-piperidine(fenpropidin), N-tridecyl-2,6-dimethyl-morpholine (tridemorph),N-dodecyl-2,6-dimethyl-morpholine (aldimorph),2-[2-(2,4-dichlorophenyl)-2-(2-propenyloxy)-ethyl]-imidazole (imazalil),N-[2-(2,4,6-trichlorophenoxy)-ethyl]-N-propyl-1H-imidazole (prochloraz),N-(3,5-dichlorophenyl)-1,2-dimethyl-cyclopropane-1,2-dicarboximide(procymidone), 2-methoxycarbamoyl-benzimidazole (carbendazim), methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate (benomyl),2,4-dichloro-6-(2'-chlorophenyl-amino)-1,3,4-triazine (anilazine),bis-(8-guanidino-octyl)-amine triacetate (guazatine),1-(4-chlorobenzyl)-1-cyclopentyl-3-phenyl-urea (pencycuron),6-methyl-2-oxo-1,3-dithiolo-[4,4-b]-quinoxaline (chinomethionat),1-(4-fluorophenyl)-1-(1,2,4-triazol-1-yl-methyl)-2-(2-chlorophenyl)-oxirane,2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-pentane (penconazole),1-[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl-methyl]-1H-(1,2,4-triazole)(propiconazole),1-(2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4-methyl-(1,3-dioxolan-2-yl)-methyl]1H(1,2,4-triazole),1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)-pentan-3-ol(diclobutrazole) and1-(2-chlorophenyl)-2-(1-chloro-cycloprop-1-yl)-3-(1,2,4-triazol-1-yl)-propan-2-ol.3. A process according to claim 1, wherein the agrochemically activecompound (A) is a herbicide selected from the group consistingof4-amino-6-(1,1-dimethyl-ethyl)-3-methylthio-1,2,4-triazin-5(4H)-on(metribuzin), 3-methyl-4-amino-6-phenyl-1,2,4-triazin-5(4H)-on(metamitron), N-benzthiazolyl-N-methyl-N'-methyl-urea and3-methoxycarbonyl-aminophenyl-N-(3'-methyl-phenyl)-carbamate.
 4. Aprocess according to claim 1, wherein the agrochemically active compound(A) is an insecticide selected from the group consisting of2-isopropoxy-phenyl-N-methyl-carbamate,N-(4-trifluoromethoxy-phenyl)-N'-(2-chloro-benzoyl)-urea,1-[4-(2-chloro-1,1,2-trifluoroethoxy)-phenyl]-3-(4-phenyl-1,2,5-oxadiazol-3yl)-ureaand 2-ethoxy-2,3-dihydro-3,3-dimethyl-5-benzofuranyl-methansulfonate. 5.A process according to claim 1, wherein the agrochemically activecompound istrans-4-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxo-3-thiazolidincarboxamide (hexythiazox).
 6. A process according to claim 1, whereinthe agrochemically active compound (A) is1-cyclohexyl-4,4-dimethyl-3-hydroxy-2-(1,2,4-triazol-1-yl) pent-1-ene(triapenthenol).
 7. A process according to claim 1, wherein the additive(B) is an N-alkyl-lactam (iii) of the formula (II) in whichR representsalkyl having 8, 10 or 12 carbon atoms and n represents the numbers 3, 4or
 5. 8. A process according to claim 1, wherein the additive (B) is amixture of N,N-dimethyl-alkylcarboxamides comprising an average 5% ofN,N-dimethyl-hexanecarboxamide, 50% of N,N-dimethyl-octane-carboxamide,40% of N,N-dimethyl-decanecarboxamide and 5% ofN,N-dimethyl-dodecanecarboxamide.